This invention relates in general to the process for the polymerization of allyl halides by using alkali metal silicates and alkaline earth metal silicates to react chemically with the halide, thereby producing a silicon acid which acts as a catalyst to polymerize the allyl halide, thereby producing poly (allyl halide allyl alcohol) polymers.
Various alkali metal silicates may be used in this invention such as sodium silicate, potassium silicate, and lithium silicate. Sodium silicate is the preferred alkali metal silicate due to its low cost and availability.
Various alkaline earth metal silicates may be used in this invention such as calcium silicate, magnesium silicate, cadmiun silicate, barium silicate, zinc silicate, barium silicate and mixtures thereof. Calcium silicate is the most useful alkaline earth metal silicate.
Various natural occuring silicates which contain an alkali compound and silicic acid may be used in this invention such as lead silicates, talc, asbestos, natrolite, garnet, mica, Kaolin, clay, feldspar, beryl silica, etc. and mixtures thereof. If the natural occuring silicates do not have an active silicic acid radical present, they may be washed with a dilute mineral acid to produce an active silicic acid radical. Silica may be heated in a dilute aqueous alkali metal hydroxide such as sodium hydroxide and potassium hydroxide in the ratio of 0.5 to 1 or 1 to 1 mols until the water evaporates, thereby producing a mono alkali metal silicate and an activated silica of an unknown chemical formula. For the purpose of this invention, the mixture will be known as "activated silica".
A combination of an alkali metal silicate, such as sodium silicate or potassium silicate and hydrated silica or silicoformic acid may be used in this invention. In U.S. Pat. No. 4,020,259 silicic acid in an alkali metal hydroxide aqueous solution is utilized to produce poly (allyl alcohol) polymer and poly (allyl chloride allyl alcohol) polymer.
Allyl halides may be produced by the addition of a halide to propylene. Methallyl halide may be produced by the addition of a halide to isobutylene. Other compounds with the combination -C.dbd.C--C', which is known as the allylic system, may be used. Allyl chloride is the preferred allyl halide. Various mono-olefinic allyl type mono-halide with the essential grouping of atoms which may be represented as ##STR1## wherein R is a hydrogen or a C.sub.1 to C.sub.4 alkyl group wherein X represents a halogen atom may be used. Furthermore, these compounds contain only one olefinic group of which one of the unsaturated carbon atoms contain at least one hydrogen atom per molecule. Representive examples of mono-olefinic allyl type mono-halides are such compounds as allyl chloride, allyl bromide, crotyl chloride, crotyl iodide, beta-methylallyl chloride, beta-methylallyl bromide, methyl vinyl carbinyl chloride, methyl vinyl carbinyl fluoride, alpha-dimethylallyl chloride, beta-cyclohexylallyl choride, cinnamyl chloride, beta-ethylcrotyl chloride, beta-phenylallyl bromido, alpha-dicyclohexylallyl chloride, beta-propylallyl iodide, beta-phenyl-allyl chloride, beta-cyclohexylallyl fluoride, 2 chloromethyl butene-1, 2-chloromethyl pentene-1, 2-chloromethyl hexene-1 and mixtures thereof.
Poly (allyl halide allyl alcohol) polymer, for the purpose of this invention will be the general name given the various polymers produced by this invention.
Poly (allyl halide allyl alochol) polymer may be chemically reacted with an alkali compound such as alkali metal hydroxides, oxides and carbonates to produce poly (allyl alcohol) polymers. The poly (allyl halide allyl alcohol) polymers and poly (allyl alcohol) polymers may be chemically reacted with a hydrated silicate in the presence of an alkali catalyst to produce a poly (allyl silicate allyl alcohol) polymer.
The poly (allyl halide allyl alcohol) polymers and poly (allyl alcohol) polymers may be used as adhesives, coating agents, impregnants, molding powders, in paints, in varnishes, in laminates and as an intermediate in resin production.
Poly (allyl halide allyl alcohol) polymers and poly (allyl alcohol) polymers will react chemically with dicarboxylic acids and dicarboxylic anhydrides to produce polyester resins. They will react chemically with poly-diisocyanate compounds and urethane prepolymers to produce resins and foams. They will react chemically with epoxy compounds and epoxy resins to produce resins and foams.
By using this process, allyl halide compounds may be copolymerized with other polymerable organic compounds such as allyl halides amines, epoxy compounds, isocyanates, acrylic compounds, acrylate compounds, vinyl compounds, diene compounds, allyl alcohol, aldehydes, ketones, diallylic maleates and mixtures thereof.
Allyl halide compounds may be copolymerized by this process with polymerable organic compounds to produce aqueous emulsions by using a peroxide or a redox system. Allyl halides may be copolymerized with vinyl monomers such as vinyl chloride, vinyl acetate, acrylonitrite, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, vinylidene chloride, styrene and mixtures thereof to produce poly (vinyl allyl halide allyl alcohol) copolymers. Allyl halide will copolymerize with organic dienes such as isoprene, chloroprene and butadiene by using a redox system with this process to produce poly (diene allyl halide allyl alcohol) polymers.